CN112679718B - Catalyst for preparing polycyclohexene carbonate - Google Patents
Catalyst for preparing polycyclohexene carbonate Download PDFInfo
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- CN112679718B CN112679718B CN202011577039.1A CN202011577039A CN112679718B CN 112679718 B CN112679718 B CN 112679718B CN 202011577039 A CN202011577039 A CN 202011577039A CN 112679718 B CN112679718 B CN 112679718B
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Abstract
The invention discloses an application of a zinc picolinate complex catalyst in preparation of cyclohexene carbonate, wherein the catalyst is prepared from pyridinedicarboxylic acid (substituted pyridinedicarboxylic acid) and zinc acetate [ Zn (OAc) 2 ·2H 2 O]The pyridine carboxylic acid zinc complex is prepared by the reaction. The catalyst is used for catalyzing the copolymerization of carbon dioxide and cyclohexene oxide under the conditions of 50-170 ℃ and 0.5-5.5 MPa of carbon dioxide pressure to obtain the polycarbonate cyclohexene ester with different molecular weights, the alternating copolymerization rate of the carbon dioxide and the cyclohexene oxide is more than 97%, and the catalytic efficiency reaches 1175 g of polymer/g of zinc.
Description
Technical Field
The invention relates to a pyridine-ring-containing zinc carboxylate complex catalyst applied to preparation of aliphatic polycarbonate, in particular to application of the pyridine-ring-containing zinc carboxylate complex catalyst in preparation of cyclohexene carbonate by catalyzing reaction of carbon dioxide and cyclohexene oxide.
Background
Chemical fixation of carbon dioxide is one of the effective methods for reducing carbon dioxide emission and protecting the environment. Particularly, the aliphatic polycarbonate prepared by the reaction of the carbon dioxide and the epoxy compound has the advantages of simple operation, abundant raw materials and low cost, and is an effective way for chemically fixing the carbon dioxide with low pollution and environmental friendliness. The aliphatic polycarbonate not only has light and biodegradability, but also is an excellent oxygen and water barrier material. Therefore, it is used as a biodegradable material, a disposable medical and food packaging material, an adhesive, a working plastic, a composite material, and the like. However, since carbon dioxide has high activation energy and low reactivity, the development of a high-performance catalyst for catalyzing the reaction of carbon dioxide is a major research point in this field.
Since Inoue et al used ZnEt2-H2O system to catalyze the reaction of carbon dioxide and epoxy compound to synthesize aliphatic polycarbonate (U.S. Pat. No. 3,585,168), zinc carboxylate, zinc (cadmium) phenoxide, and aliphatic Polycarbonate (PC) were reported in sequence,
The catalyst system can be used for catalyzing carbon dioxide to react with epoxy compounds to prepare aliphatic polycarbonate (coats G W, et al, angew Chem Int Ed, 2004, 43, 6618; sakakura T, et al, chem Rev, 2007, 107, 2365.
Et al (U.S. Pat. No. 5,026,676) report that complexes such as zinc glutarate and zinc adipate prepared in the presence of organic solvent catalyze the copolymerization of carbon dioxide and propylene oxide with the highest catalytic efficiency of 26 g polymer/g catalyst. The zinc glutarate catalytic system prepared by Moon et al (US 7, 405, 265) catalyzes the copolymerization of carbon dioxide and propylene oxide, and the catalytic efficiency reaches 77 g of polymer/g of catalyst. Membenzbetween (US 6, 844, 287) prepared supported zinc glutarate catalyst system has a catalytic efficiency of 358.8 g polymer/g zinc.
The CO2 and ethylene oxide were CO-polymerized using a catalyst made from isophthalic acid and ZnO with a catalytic efficiency of 0.87 grams polymer/gram catalyst (Inoue s., makromol. Chem., rapid commun.,1980, 115, 775). The 2, 2 '-biphenyldicarboxylic acid zinc catalyst prepared from 2, 2' -biphenyldicarboxylic acid and zinc acetate is used for catalyzing the copolymerization of carbon dioxide and cyclohexene oxide, and the catalytic efficiency is 653 g of polymer/g of zinc (CN 101058636). The o-carboxybenzaldehyde o-aminophenol zinc complex catalyst prepared from o-carboxybenzaldehyde, o-aminophenol and zinc acetate is used for catalyzing copolymerization of carbon dioxide and cyclohexene oxide, and the catalytic efficiency is 1014g of polymer/g of zinc (CN 101780419B). The catalytic efficiency of the 5-methyl salicylaldehyde condensation zinc anthranilate complex catalyst prepared by adopting 5-methyl salicylaldehyde, anthranilic acid and zinc acetate [ Zn (OAc) 2.2H2O ] is 893 g of polymer/g of zinc (CN 101768261A). The catalytic efficiency of the binuclear aromatic carboxylic acid zinc complex catalyst is 1248 g of polymer/g of zinc (CN 104725406B).
Disclosure of Invention
The invention aims to provide a catalyst for catalyzing the copolymerization of carbon dioxide and an epoxy compound to prepare aliphatic polycarbonate, which has a simple preparation method and does not use an organic solvent, and a use method thereof.
The technical scheme of the invention is as follows:
a zinc pyridine (substituted pyridine) dicarboxylate complex catalyst for preparing polycyclohexene carbonate is a zinc pyridine dicarboxylate complex or a substituted zinc pyridine dicarboxylate complex, and has the following structural characteristics:
carboxyl in the catalyst has two forms of coordination, namely bidentate coordination and carbonyl oxygen coordination; the central ion Zn is respectively connected with two N, two carbonyl O and two carboxyl O in a six-coordination mode.
Wherein R is H, CH3, OCH3, (CH 3) 3C, (CH 3) 2CH, cl, br or NO2; n represents the coordination number of the complex, the numerical value represents the multi-unit polymerization number of basic structural units of the complex, and n =2 to 200, wherein n is preferably 2 to 50.
The substituted zinc picolinate complex catalyst can be a zinc 4-picolinate complex, a zinc 4-methoxypyridindicarboxylate complex, a zinc 4-tert-butylpyridindicarboxylate complex, a zinc 4-isopropylpyridinedicarboxylate complex, a zinc 4-chloropyridindicarboxylate complex, a zinc 4-nitropyridindicarboxylate complex, or a zinc 4-bromopyridinedicarboxylate complex. Zinc picolinate complexes or zinc 4-methoxypyridinedicarboxylate complexes are preferred in the present invention.
Reference to the preparation of catalysts (n. Okabe, n. Oya, acta crystalloger Set C2000, 56, 305.): 0.73g (4.4 mmol) of 2, 6-pyridinedicarboxylic acid was weighed and dissolved in 50mL of hot water, 5mL of an aqueous solution containing 0.48g (2.2 mmol) of zinc acetate [ Zn (OAc) 2.2H2O ] was added, a white precipitate was formed by cooling, and the solution was filtered and washed, and vacuum-dried at 80 ℃ for 24 hours to obtain 0.86g of zinc dipicolinate [ Zn (dipicolH) 2] 3H2O with a yield of 86.3%.
The method for preparing the cyclohexene carbonate by using the catalyst provided by the invention is that the dosage of the catalyst is that the molar weight ratio of cyclohexene oxide is 1/500-1/5000, the reaction temperature is 50-170 ℃, the reaction pressure is 0.5-5.5 MPa, and the reaction time is 10-100 h.
Compared with the prior art, the invention has the advantages that the preparation method of the catalyst is simple, no organic solvent is used in the preparation process, the structure is stable, the catalytic efficiency is up to 1262.7 g of polymer/g of zinc, and the alternating polymerization rate of the catalytic product of the polycyclohexene carbonate is up to 98.2%.
Detailed Description
The present invention is further described below with reference to the following examples, but is not limited thereto.
Example 1
Putting 0.10g of zinc picolinate complex catalyst and a stirrer into a pre-dried 100mL stainless steel high-pressure reaction kettle, heating to 120 ℃, vacuum-drying for 5h, introducing a certain amount of carbon dioxide, cooling to room temperature and normal pressure, adding 22mL (21.1 g) cyclohexene oxide into the reaction kettle by using a glass syringe, introducing the carbon dioxide, keeping the pressure at 4.0MPa, magnetically stirring at 110 ℃ for reaction for 72h, stopping the reaction, and cooling to room temperature.
Taking out the reactant, carrying out reduced pressure distillation to recover unreacted cyclohexene oxide, dissolving the residue with a proper amount of dichloromethane, slowly dropwise adding the dissolved residue into sufficient methanol stirred at a high speed to precipitate a high polymer, and filtering, washing with methanol and drying in vacuum to obtain 18.3g of polycyclohexene carbonate. The average molecular weight was determined by gel permeation chromatography to be 10700, and 1H NMR analysis showed an alternating copolymerization ratio of carbon dioxide and cyclohexene oxide of 98.2% and a catalytic efficiency of 1262.7 g polymer/g zinc.
Example 2
Using the same apparatus and under the same initial conditions as used in example 1, an amount of cyclohexene oxide added was 22mL (21.1 g), and the reaction pressure was maintained at 4.0MPa at 100 ℃ for 72 hours to give 17.03g of an aliphatic polycarbonate having an average molecular weight of 97000, an alternating copolymerization rate of carbon dioxide and cyclohexene oxide of 98.0%, and a catalytic efficiency of 1175.1 g of polymer/g of zinc.
Example 3
In the same apparatus as used in example 1, an amount of cyclohexene oxide added was 22mL (21.1 g) under the same conditions, and a reaction pressure of 4.0MPa was maintained at 90 ℃ for 72 hours to give 4.15g of an aliphatic polycarbonate having an average molecular weight of 113000 and an alternating copolymerization rate of carbon dioxide and cyclohexene oxide of 98.1% and a catalytic efficiency of 282.2 g of polymer/g of zinc.
Example 4
In the same apparatus as used in example 1, cyclohexene oxide was added in an amount of 20mL (19.2 g) under the same conditions, and the reaction was carried out at 90 ℃ under a pressure of 4.0MPa for 72 hours to give 4.15g of an aliphatic polycarbonate having an average molecular weight of 113000 and an alternating copolymerization rate of carbon dioxide and cyclohexene oxide of 98.2% and a catalytic efficiency of 282.2 g of polymer/g of zinc.
Example 5
In the same apparatus as used in example 1, an amount of cyclohexene oxide added under the same conditions was 20mL (19.2 g), and the reaction was carried out at 90 ℃ under a pressure of 3.0 MPa for 60 hours to give 4.15g of an aliphatic polycarbonate having an average molecular weight of 113000 and an alternating copolymerization rate of carbon dioxide and cyclohexene oxide of 98.2% and a catalytic efficiency of 282.2 g of polymer/g of zinc.
Example 6
In the same apparatus as used in example 1, cyclohexene oxide was added in an amount of 15mL (14.4 g) under the same conditions, and the reaction was carried out at 110 ℃ under a pressure of 3.8 MPa for 48 hours to give 8.93g of an aliphatic polycarbonate having an average molecular weight of 90000, an alternating copolymerization rate of carbon dioxide and cyclohexene oxide of 97.8% and a catalytic efficiency of 616.2 g of polymer/g of zinc.
Example 7
In the same apparatus as used in example 1, cyclohexene oxide was added in an amount of 10 mL (9.6 g) under the same conditions, and the reaction was carried out at 100 ℃ under a pressure of 4.5 MPa for 50 hours to give 7.18g of polycyclohexene carbonate having an average molecular weight of 87000 and an alternating copolymerization ratio of carbon dioxide and cyclohexene oxide of 98.1% and a catalytic efficiency of 495.4 g polymer/g zinc.
Example 8
In the same apparatus as used in example 1, under the same conditions, the zinc picolinate complex catalyst was changed to a zinc 4-methoxypyridinedicarboxylate complex catalyst in an amount of 0.1g and cyclohexene oxide in an amount of 25ml (24.0 g), and the mixture was reacted at 4.0MPa and 105 ℃ for 58 hours to give 16.3g of an aliphatic polycarbonate having an average molecular weight of 105000 and an alternating copolymerization rate of carbon dioxide and cyclohexene oxide of 97.4% and a catalytic efficiency of 1126 g of polymer/g of zinc.
Example 9
In the same apparatus as used in example 1, under the same conditions, the zinc picolinate complex catalyst was changed to a zinc 4-picolinate complex catalyst in an amount of 0.1g, and cyclohexene oxide was added in an amount of 17mL (16.3 g), and the reaction was carried out at 95 ℃ under a pressure of 2.0MPa for 48 hours to give 6.3g of an aliphatic polycarbonate having an average molecular weight of 110000 and a copolymerization rate of alternating carbon dioxide and cyclohexene oxide of 98.3% with a catalytic efficiency of 501 g polymer/g zinc.
TABLE 1 yield and catalytic efficiency of polymers under different catalysts, reaction conditions
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed.
Claims (6)
1. The application of the catalyst for preparing the aliphatic polycarbonate by using the zinc picolinate complex is characterized in that the catalyst is a zinc picolinate complex or a substituted zinc picolinate complex, and the catalyst is applied to catalyzing copolymerization of carbon dioxide and cyclohexene oxide to prepare polycyclohexene carbonate;
the catalyst is a zinc pyridinedicarboxylate complex or a substituted zinc pyridinedicarboxylate complex, and has the following structural characteristics:
carboxyl in the catalyst has two forms of coordination, namely bidentate coordination and carbonyl oxygen coordination; the central ion Zn is respectively connected with two N, two carbonyl O and two carboxyl O in a six-coordination mode; wherein R is H, CH 3 、OCH 3 、 (CH 3 ) 3 C、(CH 3 ) 2 CH. Cl, br or NO 2 (ii) a n represents the coordination number of the complex, and the numerical value represents the multi-unit polymerization number of the basic structural unit of the complex; wherein n is 2 to 50.
2. The use of the zinc pyridinedicarboxylate complex catalyst according to claim 1, wherein the substituted zinc pyridinedicarboxylate complex catalyst is selected from the group consisting of zinc 4-picolinate complex, zinc 4-methoxypyridinate complex, zinc 4-tert-butylpyridinate complex, zinc 4-isopropylpyridinedicarboxylate complex, zinc 4-chloropyridinate complex, zinc 4-nitropyridinate complex, and zinc 4-bromopyridinedicarboxylate complex.
3. The use of a zinc picolinate complex catalyst as claimed in claim 1, wherein the zinc picolinate complex catalyst is a zinc picolinate complex or a zinc 4-methoxypicolinate complex.
4. The use of the zinc pyridinedicarboxylate complex catalyst according to claim 1, wherein no solvent is used in the reaction process to produce the polycyclohexene carbonate.
5. The use of a zinc pyridinedicarboxylate complex catalyst for producing aliphatic polycarbonates as claimed in claim 1, wherein the molar ratio of the amount of catalyst to cyclohexene oxide used in the production of the polycyclohexene carbonate is from 1/500 to 1/5000.
6. The use of the zinc pyridinedicarboxylate complex catalyst according to claim 1 for producing aliphatic polycarbonates, wherein the reaction temperature is 50 to 170 ℃, the initial pressure of carbon dioxide is 0.5 to 5.5MPa, and the reaction time is 10 to 100 hours.
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Citations (5)
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| CN101058636A (en) * | 2007-06-05 | 2007-10-24 | 郑州大学 | Catalyst for aliphatic polycarbonate polymerization, preparation method and use method thereof |
| CN101768261A (en) * | 2010-02-10 | 2010-07-07 | 河南天冠新型生物材料有限公司 | Application of aromatic zinc carboxylate complex catalyst for preparing aliphatic polycarbonate |
| CN107641197A (en) * | 2017-10-30 | 2018-01-30 | 河南工程学院 | A kind of copolyreaction catalyst using carbon dioxide with 7-oxa-bicyclo[4.1.0 as monomer |
| CN107722254A (en) * | 2017-10-30 | 2018-02-23 | 河南工程学院 | The catalyst and catalysis process of fatty poly-ester carbonate are prepared for carbon dioxide and cyclohexene oxide reaction |
| CN107954973A (en) * | 2017-12-06 | 2018-04-24 | 河南工程学院 | A kind of method that zinc based catalyst prepares cyclic carbonate |
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2020
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101058636A (en) * | 2007-06-05 | 2007-10-24 | 郑州大学 | Catalyst for aliphatic polycarbonate polymerization, preparation method and use method thereof |
| CN101768261A (en) * | 2010-02-10 | 2010-07-07 | 河南天冠新型生物材料有限公司 | Application of aromatic zinc carboxylate complex catalyst for preparing aliphatic polycarbonate |
| CN107641197A (en) * | 2017-10-30 | 2018-01-30 | 河南工程学院 | A kind of copolyreaction catalyst using carbon dioxide with 7-oxa-bicyclo[4.1.0 as monomer |
| CN107722254A (en) * | 2017-10-30 | 2018-02-23 | 河南工程学院 | The catalyst and catalysis process of fatty poly-ester carbonate are prepared for carbon dioxide and cyclohexene oxide reaction |
| CN107954973A (en) * | 2017-12-06 | 2018-04-24 | 河南工程学院 | A kind of method that zinc based catalyst prepares cyclic carbonate |
Non-Patent Citations (2)
| Title |
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| Copper(II) and zinc(II) complexes of pyridine-2,6-dicarboxylic acid;Nobuo Okabe 等;《Acta Crystallographica Section C》;20001231;第305-307页 * |
| Green and selective oxidation reactions catalyzed by kaolinite covalently grafted with Fe(III) pyridine-carboxylate complexes;Emerson H.de Faria等;《Catalysis today》;20120103;第135-149页 * |
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